4-Bromoanisole → HCID 22290103, compound

HRID 1270017Notes

Reaction equation

HRID 1270017 reaction equation
[Mg].Br[C:3]1[CH:8]=[CH:7][C:6]([CH3:9])=[CH:5][CH:4]=1.Br[C:11]1[CH:16]=[CH:15][C:14]([O:17][CH3:18])=[CH:13][CH:12]=1.[P:19](Cl)(Cl)(Cl)=[O:20]>BrCCBr.O1CCCC1>[CH3:18][O:17][C:14]1[CH:15]=[CH:16][C:11]([P:19](=[O:20])([C:11]2[CH:16]=[CH:15][C:14]([O:17][CH3:18])=[CH:13][CH:12]=2)[C:3]2[CH:8]=[CH:7][C:6]([CH3:9])=[CH:5][CH:4]=2)=[CH:12][CH:13]=1

Participants

7

Reactant 4

HCID 77304-BromoanisoleHCID 78054-BromotolueneHCID 24813Phosphorus oxychlorideHCID 5462224Magnesium

Product 1

HCID 22290103HCID 22290103, compoundYield 83%

Reagents, catalysts & solvents 2

HCID 78391,2-DibromoethaneCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
67 °C

Procedure

Magnesium (1430 g, 58.8 mol), tetrahydrofuran (12 L), and 1,2-dibromoethane (2.2 g, 0.012 mol) were stirred under nitrogen for 1 h. The mixture was then heated to reflux and the heating stopped. A mixture of 4-bromotoluene (3268 g, 19.1 mol) and 4-bromoanisole (7150 g, 38.2 mol) was added at a rate to maintain a slow reflux (67° C.) over a period of 4 h. The reaction mixture was then held for a further 5 h at 70° C. Phosphorus oxychloride (2930 g, 19.1 mol) was added at a rate to maintain a temperature of 70° C. (5 h). The reaction was then held at 70° C. for a further 5 h. The reaction mixture was then worked up to give the product mixture (5563.8 g, 83%) as an amber colored oil upon concentration. 31P NMR: (d6-DMSO) δ 27.3 (s), 27.1 (s), 26.9 (s), 26.9 (s), 26.7 (s). GC (area %): tris(4-methylphenyl)phosphine oxide 3.8%, bis(4-methylphenyl)(4-methoxyphenyl)phosphine oxide 21.0%, bis(4-methoxy-phenyl)(4-methylphenyl)phosphine oxide 39.4%, and tris(4-methoxyphenyl)-phosphine oxide 25.1%.

Workup

  1. temperatureThe mixture was then heated
  2. temperatureto reflux
  3. additionwas added at a rate
  4. temperatureto maintain
  5. temperatureto maintain a temperature of 70° C. (5 h)
  6. waitThe reaction was then held at 70° C. for a further 5 h

Sources & evidence

ORD record
ord-2316d0180e5d4bb584e301bbccc98ef3
Source dataset
uspto-grants-2007_04
Patent number
US07201957B2

Reaction notes

Loading…